WO2012053655A1

WO2012053655A1 - Structure coated with polysiloxane-containing nano structure complex, and process for production thereof

Info

Publication number: WO2012053655A1
Application number: PCT/JP2011/074376
Authority: WO
Inventors: 金　仁華; 建軍袁
Original assignee: 一般財団法人川村理化学研究所
Priority date: 2010-10-20
Filing date: 2011-10-18
Publication date: 2012-04-26
Also published as: JPWO2012053655A1; JP5028549B2

Abstract

Provided are: a structure coated with a polysiloxane-containing nano structure complex, which comprises a nano structure complex that is produced by complexing a polymer containing a linear polyethyleneimine skeleton with organopolysiloxane to form a structure unit having a nano-meter-order size and a base material that has a surface coated with the nano structure complex; and a process for producing the structure. The process is characterized by comprising the steps of: (1) immersing a solid base material (X) in a solution that contains a polymer (A) having a polyethyleneimine skeleton (a) and then removing the solid base material (X) from the solution to thereby form a polymer layer on the surface of the solid base material (X); and (2) bringing the solid base material (X) having the polymer layer, which is produced in step (1), into contact with a 0.05- to 0.5-vol% solution of an organoalkoxysilane (B') for 5 hours or longer to cause the precipitation of organopolysiloxane (B) in the polymer layer that has been formed on the surface of the solid base material (X) to thereby form a nano structure complex (Y).

Description

Polysiloxane-containing nanostructure composite-coated structure and method for producing the same

In the present invention, a solid substrate surface having an arbitrary shape is densely coated with a nanostructure composite (composite nanofiber or composite nanoparticle) in which a polymer having a polyethyleneimine skeleton and an organopolysiloxane are combined on the nanometer order. The present invention relates to a polysiloxane-containing nanostructure composite-covered structure and a method for producing the structure.

Biosilica, which inhabits the natural world, coats its cell surface with a silica shell patterned in nano and micro dimensions, and operates life in fresh water and seawater. Since the structure pattern of the silica shell is very complicated and sophisticated, research on imitating biosilica is active from the material viewpoint. In particular, since a polyamine plays an important role in the formation of a silica shell of biosilica, the construction of a structure that is covered with a thin film of silica or titanium oxide using polyamine has attracted attention.

Against the background of the above circumstances, the present inventors disclosed a structure of a silica or titanium oxide nanostructure composite coating using linear polyethyleneimine (see Non-Patent Documents 1 and 2 and Patent Documents 1 and 2). . The method is, for example, a simple method of forming a linear polyethyleneimine crystalline thin film on the surface of a substrate and then immersing it in a silica source or titanium oxide source solution to obtain the structure. The object is a structure that is densely covered with a silica-based or titanium oxide-based nanostructure composite having a complicated hierarchical structure.

On the other hand, coating technology that uses organopolysiloxane as a component has developed dramatically over the past 20 years, and it has become an industrial technology as an outstanding technology with low volatility, high strength, toughness, and strong organic / inorganic composite coating. Many related patents have been filed (see, for example, Patent Documents 3 to 6). In addition, a method for producing a nanospatial laminated film containing organopolysiloxane as a main component has also been developed (see, for example, Non-Patent Document 3). However, nano-surface construction technology and nano-structure thin film construction technology using organopolysiloxane nanostructures, for example, nanofibers as basic structural units, have not been developed.

Silica is a hard and brittle inorganic material, but organopolysiloxane has many organic polymer properties, so it exhibits soft and tough physical properties. In addition, since the organopolysiloxane itself contains an organic functional group, various functions can be expressed on the surface of the nanostructure. Therefore, developing a structure formed by coating an organopolysiloxane composite having a nanostructure is a challenging problem in the nanosurface / nanointerface technology.

JP 2009-057263 A JP 2009-203120 A JP 2010-083946 A JP 2010-066518 A JP 2009-042422 A JP 2008-285651 A

The problem to be solved by the present invention is a structure in which a solid substrate surface of an arbitrary shape is coated with a nanostructure containing a polysiloxane, in particular, a polyamine and an organopolysiloxane are combined in a nanometer order. The resulting nanostructure composite is spread over the entire surface of the substrate, forming a nanostructure with a complex structure on the substrate as a coating that completely covers the substrate. An object of the present invention is to provide a covering structure and a simple and efficient method for manufacturing the structure.

The present inventors have already made use of the feature that a polymer having a polyethyleneimine skeleton forms a nanocrystalline thin film on the surface of an arbitrary substrate, and contacting the crystalline thin film with a silica source or a titanium oxide source solution. In addition, a nanostructure composite of silica or titanium oxide was selectively deposited on the surface of the substrate, and a structure coated with a film having a complicated nanostructure and a method for producing the structure were provided (Patent Documents 1 to 5). 2).

Such a conventional silica or titanium oxide-coated structure by the present inventor uses a raw material such as tetraalkoxysilane, which undergoes hydrolysis and condensation reaction (sol-gel reaction) on the surface of the polyethyleneimine crystal film. And a completely inorganic composition, that is, an inorganic composition represented by SiO ₂ and TiO ₂ .

On the other hand, for the construction of a non-silica (non-inorganic) structure, it is not tetraalkoxysilane or the like that is used as a raw material, but an organoalkoxy having a Si—C bond structure in which at least two carbon atoms are bonded to a silicon atom. silane _{_{_{{R n Si (OCH 3)}}} 4-n or _{_{_{_{R n Si (OCH 2 CH 3}}}} ) 4-n, R is a hydrocarbon group which may have a substituent group, n = 1 or 2} using the Is considered necessary.

Usually, tetraalkoxysilane, which is a silica source, is rapidly hydrolyzed and silica is rapidly formed. Therefore, in the manufacturing method provided in Patent Document 1, the silica structure is transferred on the nanocrystal thin film composed of the polyethyleneimine skeleton-containing polymer layer on the surface of the substrate without being damaged. In comparison, it grows slowly into a polymer composed of hydrolyzed organoalkoxysilane and a stable siloxane bond. Therefore, the nanocrystal thin film on the surface of the base material may be peeled off from the base material and dissolved in the medium, or the nanocrystal structure may be destroyed. As a result, the formation of the organopolysiloxane-containing nanostructure is likely to be greatly inhibited.

In the present invention, the hydrolytic condensation reaction of organoalkoxysilane efficiently proceeds on the surface of a crystalline thin film made of a polymer containing a polyethyleneimine skeleton, and it grows into a stable nanostructure of organopolysiloxane. An optimum method for forming a nano-film structure completely covering the substrate surface has been established, and the present invention has been completed.

That is, the present invention provides an organopolysiloxane and a polyethyleneimine skeleton-containing polymer by hydrolytic condensation of an organoalkoxysilane on a polymer thin film having a polyethyleneimine skeleton formed on the surface of a solid substrate. The present invention provides a structure coated with a composite nanostructure and a method for producing the same.

The organopolysiloxane-containing nanostructure composite-coated structure of the present invention comprises a polymer having a polyethyleneimine skeleton and an organopolysiloxane on the surface of a solid substrate such as metal, glass, inorganic metal oxide, plastic, and cellulose of any shape. And the structure itself may be in any form such as a complex plane, curved surface, rod, tube, etc., and in the tube, outside the tube, in the container Any of the outside of the container can be limitedly or comprehensively coated. In addition, since the nanostructure composite to be coated uses a polymer layer formed on the base material by contact between the polymer solution having a polyethyleneimine skeleton and the solid base material, only a part of the surface of the solid base material is used. It is easy to select and coat. Regardless of the size of the structure, since the nanostructure composite is formed on the surface, the surface area per unit area (specific surface area) becomes extremely large. In addition, since the nanostructure composite on the surface of the solid substrate is basically an organopolysiloxane, its heat resistance, solvent resistance, acid resistance, and alkali resistance are strong, and relatedly, the corrosion resistance is also strong. Further, since it is an organopolysiloxane, the viscoelasticity of this nanostructure film is superior to that of silica, and it can withstand certain friction and wear from brittle silica. A structure having a nano surface provided with such physical properties can immobilize functional sites such as catalysts, metal nanoparticles, drugs, and dyes. Also, various high / low refractive index materials, optical materials such as color developing properties and light emitting elements can be fixed on the surface. Furthermore, a super water-repellent function on the surface of the nanostructure due to the hydrophobicity of the aliphatic and aromatic groups in the organopolysiloxane is also exhibited. Accordingly, the organopolysiloxane-containing nanostructure composite coating structure of the present invention can be widely applied industrially.

It is a scanning electron micrograph of the structure obtained in Example 1-1. Left) Photo taken from above; Right) Photo taken from the side (interface between glass and composite). It is a scanning electron micrograph of the structure obtained in Example 1-2. Left) Photo taken from above; Right) Photo taken from the side (interface between glass and composite). It is a scanning electron micrograph of the structure obtained in Example 1-3. Left) Photo taken from above; Right) Photo taken from the side (interface between glass and composite). It is a scanning electron micrograph of the structure obtained in Example 2-1. a) Photograph with low resolution observed from above; b) Enlarged view of part of a; c) Photograph from lateral direction (interface between glass and composite). It is a scanning electron micrograph of the structure obtained in Example 2-2. a) Photograph with low resolution observed from above; b) Enlarged view of part of a; c) Photograph from lateral direction (interface between glass and composite). It is a scanning electron micrograph of the structure obtained in Example 2-3. a) Photograph with low resolution observed from above; b) Enlarged view of part of a; c) Photograph from lateral direction (interface between glass and composite). It is a scanning electron micrograph of the structure obtained in Example 2-4. a) Photograph with low resolution observed from above; b) Enlarged view of part of a; c) Photograph from lateral direction (interface between glass and composite). It is a scanning electron micrograph of the structure obtained in Example 3-1. a) Photograph of low resolution observed from above; b) Enlarged view of part of a. It is a scanning electron micrograph of the structure obtained in Example 3-2. a) Low-resolution photograph observed from above; b) Enlarged view of part of a; c) Enlarged view of part of b; d) Photograph from the lateral direction (interface between glass and composite). It is a scanning electron micrograph of the structure obtained in Example 4-1. a) Low-resolution photograph observed from above; b) Enlarged view of part of a; c) Enlarged view of part of b; d) Photograph from the lateral direction (interface between glass and composite). It is a scanning electron micrograph of the structure obtained in Example 4-2. a) Low-resolution photograph observed from above; b) Enlarged view of part of a; c) Enlarged view of part of b; d) Photograph from the lateral direction (interface between glass and composite). 6 is a scanning electron micrograph of the structure obtained in Example 5. FIG. a) Low-resolution photograph observed from above; b) Enlarged view of part of a; c) Enlarged view of part of b; d) Photograph from the lateral direction (interface between glass and composite). 6 is a scanning electron micrograph of the structure obtained in Example 6. FIG. a) Photograph of low resolution observed from above; b) Enlarged view of part of a; c) Enlarged view of part of b. 2 is a scanning electron micrograph of the nanoturf structure of the silica / polymer composite produced in Comparative Example 1. FIG. 6 is a scanning electron micrograph after the abrasion test of the structure surface obtained in Example 6. FIG. a) Photograph of low resolution observed from above; b) Enlarged view of part of a; c) Enlarged view of part of b.

In the structure of the present invention, the surface of the solid substrate (X) was coated with the nanostructure composite (Y) containing the polymer (A) having the polyethyleneimine skeleton (a) and the organopolysiloxane (B). Is. Furthermore, the structure of the present invention may contain metal ions, metal nanoparticles, or organic dye molecules in the nanostructure composite part. Therefore, the structure of the present invention essentially comprises a solid substrate, a polymer, and an organopolysiloxane, and other metal ions, metal nanoparticles, organic dye molecules, and the like as optional constituents. In the present invention, the nanostructure composite (Y) means that the polymer (A) and the organopolysiloxane (B), and metal ions, metal nanoparticles, organic dye molecules, etc. used in combination as needed are in the nanometer order. This indicates that it is an organic-inorganic composite having a certain shape such as a fiber or particle. In addition, as described later, the metal nanoparticles indicate that the metal fine particles are present in a size of the order of nanometers, and need not be completely spherical, but are described as “particles” for convenience. To do. The present invention will be described in detail below.

[Solid substrate]
The solid substrate (X) used in the present invention is not particularly limited as long as the polymer (A) having a polyethyleneimine skeleton (a) described later can be adsorbed. For example, glass, metal, metal oxide, etc. Inorganic material base material, resin (plastic), organic material base material such as cellulose, etc. Furthermore, glass, metal, metal oxide surface etched substrate, resin substrate surface plasma treatment, ozone treatment Can be used.

Although it does not specifically limit as an inorganic material type glass substrate, For example, glass, such as heat resistant glass (borosilicate glass), soda-lime glass, crystal glass, optical glass which does not contain lead and arsenic, is used suitably. Can do. In the use of a glass substrate, the surface can be used by etching with an alkaline solution such as sodium hydroxide, if necessary.

The inorganic material-based metal substrate is not particularly limited, but for example, a substrate made of iron, copper, aluminum, stainless steel, zinc, silver, gold, platinum, or an alloy thereof can be suitably used.

The inorganic material-based metal oxide substrate is not particularly limited. For example, ITO (indium tin oxide), tin oxide, copper oxide, titanium oxide, zinc oxide, alumina, and the like can be suitably used.

As the resin base material, for example, processed products of various polymers such as polyethylene, polypropylene, polycarbonate, polyester, polystyrene, polymethacrylate, polyvinyl chloride, polyethylene alcohol, polyimide, polyamide, polyurethane, epoxy resin, and cellulose can be used. it can. In the use of various polymers, the surface may be treated with plasma or ozone, or treated with sulfuric acid or alkali, if necessary.

The shape of the solid substrate (X) is not particularly limited, and may be a flat or curved plate or a film. In particular, a tubular tube, a spiral tube of a tubular tube, a microtube; a container having an arbitrary shape (for example, a spherical shape, a square shape, a triangular shape, a cylindrical shape); an arbitrary shape (for example, a cylindrical shape, (Rectangle, triangle, etc.) A rod or a solid substrate in a fiber state can also be suitably used.

[Polymer having Polyethyleneimine Skeleton (a) (A)]
In the present invention, it is essential to use a polymer (A) having a polyethyleneimine skeleton (a) for the polymer layer formed on the solid substrate (X). The polymer (A) having the polyethyleneimine skeleton (a) may be a linear, star-shaped or comb-shaped homopolymer, or a copolymer having other repeating units. In the case of a copolymer, the molar ratio of the polyethyleneimine skeleton (a) in the polymer (A) is preferably 20% or more from the viewpoint of forming a stable polymer layer. It is more preferable that it is a block copolymer having 10 or more repeating units.

The polyethyleneimine skeleton (a) may be either branched or linear, but is more preferably a linear polyethyleneimine skeleton having a high ability to form crystalline aggregates. Whether the polymer is a homopolymer or a copolymer, if the molecular weight corresponding to the polyethyleneimine skeleton is in the range of 500 to 1,000,000, a stable polymer layer is formed on the substrate (X). It is preferable because it can be formed. The polymer (A) having the polyethyleneimine skeleton (a) can be obtained from a commercially available product or a synthesis method already disclosed by the present inventors (for example, JP-A-2005-264421).

As will be described later, the polymer (A) can be used by dissolving in various solutions. At this time, in addition to the polymer (A) having the polyethyleneimine skeleton (a), the polymer (A) is compatible with the polymer (A). It can be used by mixing with other polymers. Examples of other polymers include polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, poly (N-isopropylacrylamide), polyhydroxyethyl acrylate, polymethyloxazoline, polyethyloxazoline, and polypropyleneimine. By using these other polymers, the thickness of the nanostructure composite layer on the surface of the resulting structure can be easily adjusted.

[Organopolysiloxane (B)]
A major feature of the substrate surface of the structure obtained by the present invention is that it is a nanostructure composite containing the aforementioned polymer (A) and organopolysiloxane (B). The organopolysiloxane (B) source needed to _{_{_{form, {R n Si (OCH 3}}} ) 4-n or _{_{_{_{R n Si (OCH 2 CH 3}}}} ) 4-n, R may have a substituent And a hydrocarbon group, organoalkoxysilane (B ′) represented by n = 1 or 2}. Examples of R in the formula include a mercaptopropyl group, a methyl group, a vinyl group, a glycidoxypropyl group, a phenyl group, and the like. In the case where n in the general formula is 2, R is the same. Or it may be different. When n is 1, it is generally known as a silane coupling agent (b). For example, tetramethoxysilane, oligomer of methoxysilane condensate, tetraethoxysilane, oligomer of ethoxysilane condensate can be suitably used. . Further, alkyl-substituted alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltrimethoxysilane, iso-propyltriethoxysilane, etc., 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Xylpropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptotriethoxysilane, 3,3 -Trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p -Chloromethylphenyltrimethoxysilane, p-chloromethylphenyltriethoxysilane, etc., and the compounds in which n is 2 in the above general formula include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxy A silane etc. can be mentioned. These organoalkoxysilanes (B ′) can be used alone or in combination.

[Metal ions]
The surface of the base material in the structure of the present invention is coated with a nanostructure composite (Y) composed of the above-described polymer (A) having a polyethyleneimine skeleton (a) and an organopolysiloxane (B). Metal ions can be stably taken into the nanostructure composite (Y), and therefore a nanostructure composite-coated structure containing metal ions can be obtained.

Since the polyethyleneimine skeleton (a) in the polymer (A) has a strong coordination ability with respect to metal ions, the metal ions coordinate with the ethyleneimine units in the skeleton to form a metal ion complex. The metal ion complex is obtained by coordination of a metal ion to an ethyleneimine unit. Unlike a process such as ionic bonding, the metal ion is coordinated to an ethyleneimine unit regardless of whether the metal ion is a cation or an anion. Can form a complex. Accordingly, the metal species of the metal ion is not limited as long as it can coordinate with the ethyleneimine unit in the polymer (A), and is not limited to alkali metal, alkaline earth metal, transition metal, metalloid, lanthanum metal, poly Any of metal compounds such as oxometalates may be used, and they may be used alone or in combination.

Examples of the alkali metal include Li, Na, K, Cs and the like, and examples of counter ions of the alkali metal ions include Cl, Br, I, NO ₃ , SO ₄ , PO ₄ , ClO ₄ , PF ₆ , Examples thereof include BF ₄ and F ₃ CSO ₃ .

Examples of alkaline earth metals include Mg, Ba, Ca and the like.

As a transition metal-based metal ion, even if it is a transition metal cation (M ^{n +} ), an acid group anion (MO _x ⁿ⁻ ) composed of a bond with oxygen, or an anion composed of a halogen bond ( ML _x ⁿ⁻ ) can also be suitably used. In the present specification, the transition metal refers to Sc, Y in Group 3 of the periodic table and a transition metal element in Groups 4 to 12 in the 4th to 6th periods.

Examples of transition metal cations include cations of various transition metals (M ^{n +} ), such as Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Mo, Ru, Rh, Pd, and Ag. , Cd, W, Os, Ir, Pt, Au, Hg, monovalent, divalent, trivalent or tetravalent cations. The counter anion of these metal cations may be any of Cl, NO ₃ , SO ₄ , polyoxometalates anions, or organic anions of carboxylic acids. However, for those that are easily reduced by the ethyleneimine skeleton, such as Ag, Au, and Pt, it is preferable to prepare an ionic complex by suppressing the reduction reaction, for example, by adjusting the pH to an acidic condition.

Examples of the transition metal anion include various transition metal anions (MO _x ⁿ⁻ ) such as MnO ₄ , MoO ₄ , ReO ₄ , WO ₃ , RuO ₄ , CoO ₄ , CrO ₄ , VO ₃ , NiO ₄ , UO _2. Anions and the like.

In addition, as the metal ion, the transition metal anion is a polyoxometalate immobilized in an organopolysiloxane (B) via a metal cation coordinated to an ethyleneimine unit in the polymer (A). It may be in the form of a metal compound. Specific examples of the polyoxometalates include molybdate, tungstate and vanadate in combination with a transition metal cation.

Furthermore, anions (ML _x ⁿ⁻ ) containing various metals, such as AuCl ₄ , PtCl ₆ , RhCl ₄ , ReF ₆ , NiF ₆ , CuF ₆ , RuCl ₆ , In ₂ Cl _6, etc. The coordinated anion can also be suitably used for forming an ion complex.

Further, examples of the metalloid ions include ions of Al, Ga, In, Tl, Ge, Sn, Pb, Sb, and Bi, and among them, ions of Al, Ga, In, Sn, Pb, and Tl are preferable.

Examples of the lanthanum metal ions include trivalent cations such as La, Eu, Gd, Yb, and Eu.

[Metal nanoparticles]
As described above, in the present invention, metal ions can be incorporated into the nanostructure composite (Y) in the structure. Therefore, among these metal ions, metal ions that are easily reduced by the reduction reaction can be converted into metal nanoparticles, whereby the metal nanoparticles can be contained in the composite (Y).

Examples of the metal species of the metal nanoparticles include copper, silver, gold, platinum, palladium, manganese, nickel, rhodium, cobalt, ruthenium, rhenium, molybdenum, iron, and the like, and the metal nanoparticle in the composite (Y) The particles may be one kind or two or more kinds. Among these metal species, silver, gold, platinum, and palladium are particularly preferable because the metal ions are spontaneously reduced at room temperature or in a heated state after being coordinated to the ethyleneimine unit.

The size of the metal nanoparticles in the composite (Y) can be controlled in the range of 1 to 20 nm. Further, the metal nanoparticles can be fixed to the inside or the outer surface of the nanostructure composite (Y) of the polymer (A) and the organopolysiloxane (B).

[Organic dye molecules]
In the present invention, the polyethyleneimine skeleton (a) in the nanostructure composite (Y) covering the structure is composed of a compound having an amino group, a hydroxy group, a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group, a hydrogen bond, and A physical coupling structure can be formed by electrostatic attraction. Therefore, organic dye molecules having these functional groups can be contained in the complex (Y).

As the organic dye molecule, a monofunctional acidic compound or a bifunctional or higher polyfunctional acidic compound can be suitably used.

Specifically, for example, aromatic acids such as tetraphenylporphyrin tetracarboxylic acid and pyrene dicarboxylic acid, naphthalene disulfonic acid, pyrene disulfonic acid, pyrene tetrasulfonic acid, anthraquinone disulfonic acid, tetraphenyl porphyrin tetrasulfonic acid, phthalocyanine tetra Aromatic or aliphatic sulfonic acids such as sulfonic acid and pipes (PIPES), acid yellow, acid blue, acid red, direct blue, direct yellow, direct red series azo dyes and the like can be mentioned. In addition, a dye having a xanthene skeleton, for example, rhodamine, erythrosine, and eosin dyes can be used.

[Nanostructure composite (Y) containing polymer (A) and organopolysiloxane (B)]
The nanostructure composite (Y) containing the polymer (A) and the organopolysiloxane (B) is basically a composite nanofiber (y1) of the polymer (A) and the organopolysiloxane (B). It is an aggregate of composite nanoparticles (y2), and forms various patterns or morphologies while constituting a state in which the aggregate covers the entire substrate surface. For example, turf-like (nano turf) or composite nano fiber (y1) and / or composite in which the composite nanofiber (y1) grows on the entire surface of the solid substrate with the long axis of the fiber facing substantially vertical direction A wide variety of hierarchical structures such as a sponge (nano sponge) in which the nanoparticles (y2) form a network on the entire surface of the substrate can be formed.

The thickness of the composite nanofiber (y1) of the basic unit in the higher-order structure such as the nano turf shape or the nano sponge shape is in the range of 10 to 100 nm. The length (major axis direction) of the nanoturf-like composite nanofiber (y1) can be controlled in the range of 50 nm to 10 μm.

When a network is formed on a solid substrate, that is, when a three-dimensional network structure is constructed over the entire coating layer, the basic structure is composed only of the composite nanofiber (y1). Alternatively, the composite nanoparticle (y2) alone may be used, or both may be combined. At this time, the average particle diameter of the composite nanoparticles (y2) is preferably controlled to 20 nm or less.

The thickness from the substrate when coating on the solid substrate is related to the aggregate structure of the composite nanofiber (y1) and / or the composite nanoparticle (y2), but can be varied in the range of about 50 nm to 20 μm. . In the nano-turf shape, the composite nanofiber (y1) has a strong tendency to stand up straight, the length of the fiber basically constitutes the thickness, and the length of each individual fiber is fairly uniform. It is a feature. The thickness of the nanosponge-like layer is characterized in that it is determined by the degree to which the composite nanofiber (y1) swells with a complex entanglement having regularity. When a network is formed, the thickness is determined by the overlapping state, the existence ratio of the composite nanofiber (y1) and the composite nanoparticle (y2), and the like.

In the nanostructure composite (Y), the component of the polymer (A) can be adjusted at 5 to 30% by mass. By changing the content of the polymer (A) component, the aggregate structure (higher order structure) can be changed.

Further, when a metal ion, metal nanoparticle or organic dye molecule is contained in the nanostructure composite (Y), it is possible to control the higher order structure depending on the type. Even in this case, the basic unit is the composite nanofiber (y1) and / or the composite nanoparticle (y2) as described above, which are combined to form a complex shape.

The amount of metal ions taken up when taking up metal ions is preferably adjusted within a range of 1/4 to 1/200 equivalents per 1 equivalent of ethyleneimine units in the polymer (A), and this ratio can be changed. Can change the thickness of the coating layer. In addition, the coating layer at this time may develop color depending on the metal species.

The amount of metal nanoparticles incorporated when incorporating metal nanoparticles is preferably adjusted within a range of 1/4 to 1/200 equivalent per 1 equivalent of ethyleneimine unit in the polymer (A). By changing the thickness, the thickness of the coating layer can be changed. In addition, the coating layer at this time may develop color depending on the metal species.

The organic dye molecule uptake amount when taking up the organic dye molecule is preferably prepared in the range of 1/2 to 1/1200 equivalent to 1 equivalent of the ethyleneimine unit in the polymer (A). By changing the thickness, the thickness and shape pattern of the coating layer can be changed.

Also, two or more kinds of metal ions, metal nanoparticles and organic dye molecules can be simultaneously incorporated into the nanostructure composite (Y).

[Method for producing nanostructure composite-coated structure]
The structure production method of the present invention includes a solution of a polymer (A) having a polyethyleneimine skeleton (a), a mixed solution of a polymer (A) having a polyethyleneimine skeleton (a) and a metal ion, a polyethyleneimine skeleton (a ) And a polymer (A) having a polyethyleneimine skeleton (a), a mixed solution of a metal ion and an organic dye molecule on the surface of the solid substrate (X). After the contact, the substrate (X) is taken out, and consists of a polymer (A) having a polyethyleneimine skeleton (a) on the surface of the substrate (X), and a combined metal ion and / or organic dye molecule. A step (1) for obtaining a base material on which the polymer layer is adsorbed, and the base material on which the polymer layer is adsorbed and an organoalkoxysilane (B ′) prepared at a constant concentration are brought into contact with each other for a long time. By the catalytic function of the polyethyleneimine skeleton (a) in the polymer layer adsorbed on the surface, the organopolysiloxane (B) is deposited thereon to form the nanostructure composite (Y) and coat the substrate. A manufacturing method comprising the step (2). By this method, the nanointerface consisting of polymer (A) and organopolysiloxane (B), the nanointerface consisting of polymer (A) / metal ion / organopolysiloxane (B), polymer ( A nano-interface coating layer comprising A) / organic dye molecule / organopolysiloxane (B) can be easily formed.

The polymer described above can be used as the polymer (A) having the polyethyleneimine skeleton (a) used in the step (1). In addition, the solvent that can be used for obtaining the solution of the polymer (A) is not particularly limited as long as the polymer (A) can be dissolved, and examples thereof include water, organic solvents such as methanol and ethanol, These mixed solvents can be used as appropriate.

The concentration of the polymer (A) in the solution is not particularly limited as long as the polymer layer can be formed on the solid substrate (X), but the desired pattern formation and the density of the polymer adsorbed on the substrate surface are increased. In this case, the range is preferably 0.05% by mass to 50% by mass, and more preferably 0.5% by mass to 10% by mass.

In the solution of the polymer (A) having a polyethyleneimine skeleton (a), the above-mentioned other polymers that are soluble in the solvent and compatible with the polymer (A) can be mixed. The mixing amount of the other polymer may be higher or lower than the concentration of the polymer (A) having the polyethyleneimine skeleton (a).

When forming a coating layer composed of a nanostructure composite (Y) containing metal ions, the metal ions are mixed in a solution of the polymer (A) having a polyethyleneimine skeleton (a). The concentration of the metal ion is preferably adjusted to ¼ equivalent or less of the ethyleneimine unit in the polyethyleneimine skeleton (a).

Further, when forming a coating layer composed of a nanostructure complex (Y) containing organic dye molecules, the organic dye molecules are mixed in a solution of the polymer (A) having a polyethyleneimine skeleton (a). The concentration of the organic dye molecule is preferably adjusted to ½ equivalent or less of the ethyleneimine unit in the polyethyleneimine skeleton (a).

Further, in order to produce a polymer layer in the step (1), the solid substrate (X) is brought into contact with a solution of the polymer (A). As the contact method, it is preferable to immerse the desired solid substrate (X) in the solution of the polymer (A).

In the dipping method, the base material and the solution can be brought into contact with each other by putting the base material (non-container shape) into the solution or putting the solution into the base material (container shape) according to the base material state. At the time of immersion, the temperature of the polymer (A) solution is preferably in a heated state, and a temperature of about 50 to 90 ° C. is suitable. The time for bringing the solid substrate (X) into contact with the solution of the polymer (A) is not particularly limited, and is preferably selected within a few seconds to 1 hour according to the material of the substrate (X). If the material of the base material has a strong binding ability with polyethyleneimine, for example, it may be several seconds to several minutes for glass, metal, etc. If the material of the base material is weakly binding ability with polyethyleneimine, it may be several tens of minutes to one hour. good.

After contacting the solid substrate (X) with the polymer (A) solution, the substrate is taken out of the polymer (A) solution and allowed to stand at room temperature (around 25 ° C.). A body layer is formed on the surface of the substrate (X). Alternatively, the base material (X) is taken out from the solution of the polymer (A) and then immediately put into distilled water at 4 to 30 ° C. or into an aqueous ammonia solution at room temperature to below freezing temperature, so that the spontaneous polymer (A) An aggregate layer may be formed.

As the method for contacting the surface of the solid substrate (X) with the polymer (A) solution, for example, in addition to coating with a spin coater, bar coater, applicator, etc., a method such as printing or printing with a jet printer can also be used. In particular, when the contact is made in a fine pattern, a method using a jet printer is suitable.

In the step (2), the polymer layer formed in the step (1) and the organoalkoxysilane (B ′) are brought into contact with each other to deposit the organopolysiloxane (B) on the surface of the polymer layer. A nanostructure composite (Y) with siloxane (B) is formed. Even when the polymer layer contains metal ions and / or organic dye molecules, organopolysiloxane (B) can be deposited by the same method to form the target nanostructure composite (Y).

Examples of the organoalkoxysilane (B ′) used at this time include aqueous solutions of the various silane coupling agents (b) described above, alcohol solvents such as aqueous organic solvent solutions such as methanol, ethanol, propanol, and the like. A mixed solvent solution with water can be used. At this time, it is essential that the concentration of the organoalkoxysilane (B ′) is low, and the nanostructure composite (Y) without adversely affecting the nanostructure formed by the polymer (A) on the substrate. ), The volume concentration is preferably in the range of 0.05% to 5%.

As a method of bringing the solid substrate on which the polymer (A) layer is adsorbed into contact with the organoalkoxysilane (B ′), an immersion method can be preferably used. The immersion time needs to be 5 hours or more, and preferably 5 to 24 hours, but the time can be appropriately lengthened as necessary. The temperature of the organoalkoxysilane (B ′) may be room temperature (20 to 30 ° C.) or a heated state. In the case of heating, in order to regularly deposit organopolysiloxane (B) on the surface of the solid substrate (X), it is desirable to set the temperature to 70 ° C. or lower.

By selecting the type and concentration of the organoalkoxysilane (B ′), the structure of the nanostructure composite (Y) of the organopolysiloxane (B) and the polymer (A) to be deposited can be adjusted. Accordingly, it is preferable to appropriately select the type and concentration of the organoalkoxysilane (B ′).

The formation of organopolysiloxane (B) varies greatly depending on the type of organo group bonded to silicon. Accordingly, in order to derive an organopolysiloxane (B) nanostructure composite using organoalkoxysilane (B ′) having a different molecular structure, it is preferable to set conditions in accordance with the reaction characteristics of the structure.

For example, when the organo group is a mercaptopropyl group, the concentration of the reaction solution is set to 0.3 to 0.7% (volume concentration), and the substrate immersion time is set to 15 to 20 hours. The complex can be effectively induced. When the reaction solution concentration is further reduced to 0.1 vol% or less and immersed in the solution for 15 hours or more, a film composed of a composite of nanofiber network structure can be induced.

When the organo group is a methyl group, in order to induce a nanoturf-like structure composite, the substrate immersion time should be 24 hours or longer using a low concentration solution of about 0.3 to 0.8 vol%. Required.

In addition, when the organo group is a phenyl group, the nanoturf-like complex is efficiently induced by setting the substrate soaking time in the range of 7 to 10 hours in a solution of about 0.3 to 0.8 vol%. I can do it.

Polyethyleneimine can reduce noble metal ions such as gold, platinum, silver, palladium, etc. to metal nanoparticles. Accordingly, by passing the structure coated with the nanostructure composite (Y) obtained in the above step with the aqueous solution of the noble metal ion, the noble metal ion is brought into the nanostructure composite (Y). Can be converted into metal nanoparticles, and a nanostructure composite-coated structure having metal nanoparticles can be obtained.

In the above step, the dipping method can be preferably used as the method of contacting with an aqueous solution of noble metal ions. As the aqueous solution of noble metal ions, aqueous solutions of chloroauric acid, sodium chloroaurate, chloroplatinic acid, sodium chloroplatinate, silver nitrate and the like can be suitably used, and the aqueous solution concentration of noble metal ions is 0.1 to 5 mol. % Is preferred.

The temperature of the aqueous solution of noble metal ions is not particularly limited and may be in the range of room temperature to 90 ° C. However, in order to promote the reduction reaction, it is preferable to use a heated aqueous solution of 50 to 90 ° C. The time for immersing the structure in the aqueous solution of metal ions may be 0.5 to 3 hours, and about 30 minutes is sufficient when immersed in the heated aqueous solution.

In the case of a metal ion that is difficult to reduce with polyethyleneimine alone, a step of bringing the metal ion in the structure having the metal ion obtained above into contact with a reducing agent, particularly a low molecular weight reducing agent solution or hydrogen gas, In combination, by reducing the metal ions, a nanostructure composite-covered structure containing the metal nanoparticles can be obtained.

Examples of the reducing agent that can be used at this time include ascorbic acid, aldehyde, hydrazine, sodium borohydride, ammonium borohydride, hydrogen, and the like. When reducing metal ions using a reducing agent, the reaction can be carried out in an aqueous medium. The structure containing the metal ions is immersed in the reducing agent solution or left in a hydrogen gas atmosphere. Can be used. At this time, the temperature of the reducing agent aqueous solution may be in the range of room temperature to 90 ° C., and the concentration of the reducing agent is preferably 1 to 5 mol%.

The metal species of the metal ion that can be adapted to the above process is not particularly limited, but copper, manganese, chromium, nickel, tin, vanadium, and palladium are preferable because the reduction reaction proceeds promptly.

When the coated structure is immersed in the reducing agent aqueous solution, the reducing agent aqueous solution temperature is preferably room temperature or a heating state of 90 ° C. or less, and the concentration of the reducing agent is about 1 to 5%.

The various structures obtained by the above-mentioned method can be used for the various applications described above by removing the solvent and water by leaving them at room temperature (25 ° C.) to about 60 ° C.

Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” represents “mass%”.

[Shape analysis of nanostructures by scanning electron microscope]
The isolated and dried nanostructure was fixed to a sample support with a double-sided tape, and observed with a surface observation device VE-9800 manufactured by Keyence.

Synthesis example 1
<Synthesis of linear polyethyleneimine (L-PEI)>
<Synthesis of linear polyethyleneimine hydrochloride (LPEI · HCl)>
240 g of commercially available polyethyloxazoline (number average molecular weight 50,000, average polymerization degree 500, manufactured by Aldrich) was dissolved in 1500 mL of 5M aqueous hydrochloric acid. The solution was heated to 90 ° C. in an oil bath and stirred at that temperature for 10 hours. Acetone 50 mL was added to the reaction solution to completely precipitate the polymer, which was filtered and washed three times with methanol to obtain white polyethyleneimine hydrochloride powder. The yield after drying at room temperature (20 to 25 ° C.) was 178 g. When the obtained powder was identified by ¹ H-NMR (JEOL JNM-LA300 type nuclear magnetic resonance absorption spectrum measuring apparatus: heavy water), the peak derived from the side chain ethyl group of polyethyloxazoline was 1.2 ppm (CH ₃ ). And 2.3 ppm (CH ₂ ) were completely eliminated. That is, it was shown that polyethyloxazoline was completely hydrolyzed and converted to polyethyleneimine.

10 g of the powder obtained above was dissolved in 15 mL of distilled water, and 100 mL of 15% aqueous ammonia was added dropwise to the solution while stirring. The mixture was allowed to stand overnight, and then the precipitated polymer aggregate powder was filtered, and the polymer aggregate powder was washed three times with cold water. The washed crystal powder was dried at room temperature in a desiccator to obtain linear polyethyleneimine (L-PEI). The yield was 8.7 g (including crystal water). In polyethyleneimine obtained by hydrolysis of polyoxazoline, only the side chain reacts and the main chain does not change. Therefore, the polymerization degree of L-PEI is the same as 5,000 before hydrolysis.

Examples 1-1 to 1-3
[Structure in which inner wall of glass tube is coated with polymer / organopolysiloxane nanostructure composite]
Polymer L-PEI obtained in Synthesis Example 1 was added to distilled water and heated to 80 ° C. to prepare a 3% aqueous solution. A glass tube made of soda lime (inner diameter 6 mm, length 5 cm) and a syringe are connected with a rubber tube, and the heated polymer aqueous solution is sucked into the glass tube up to a certain standard, and then allowed to stand for 30 seconds. The polymer aqueous solution was discharged by a pushing force of a syringe. By this operation, an L-PEI polymer layer was formed on the inner wall of the glass tube. The glass tube was allowed to stand at room temperature for 5 minutes, and then immersed in an aqueous solution (room temperature: 25 to 30 ° C.) of mercaptopropyltrimethoxysilane (STMS), a silane coupling agent described in Table 1, for 15 hours. It was. After the glass tube was taken out and the inner wall of the glass tube was washed with water, it was dried at room temperature.

The glass tube end obtained through the above process was slightly crushed, and the fragments were observed with an SEM. 1 to 3 show the results of SEM photographs of the inner surface of the produced glass tube. In either case, a dense array film having nanofibers as a unit structure was formed on the inner wall. For comparison, a glass tube without a polymer layer was immersed in an aqueous solution of mercaptopropyltrimethoxysilane (STMS) for 10 hours or more, but nothing was observed. As can be seen from the SEM picture, the surface structure changed from nano turf to network structure with decreasing STMS concentration.

Examples 2-1 to 2-4
[Structure in which inner wall of glass tube is coated with polymer / organopolysiloxane nanostructure composite]
In Example 1, except that the time for immersion in the STMS / water solution was changed, a structure in which the glass inner wall was coated was obtained in the same manner as in Example 1 (Table 2).

The glass tube end obtained through the above process was slightly crushed, and the fragments were observed with an SEM. 4 to 7 show the results of SEM photographs of the inner surface of the glass tube obtained under each condition. In the immersion for 3 hours, there was a coating of organopolysiloxane, but there was no shape development and the surface was flat. When the immersion time was 6 hours, a network structure formed from entanglement of nanofibers was obtained. When the immersion time in the STMS aqueous solution was set to 10 hours or more, a nanoturf structure was developed. From this, it was found that, when the STMS concentration is slightly increased, it is necessary to increase the immersion time in order to form the surface structure characterized by nanofibers.

Examples 3-1 to 3-2
[Structure in which inner wall of glass tube is coated with polymer / organopolysiloxane nanostructure composite]
In Example 1, a structure in which the glass inner wall was coated was obtained in the same manner as in Example 1 except that methyltrimethoxysilane (MTMS) was used instead of STMS as the silane coupling agent (Table 3). .

The glass tube end obtained through the above process was slightly crushed, and the fragments were observed with an SEM. 8 to 9 show the results of SEM photographs of the inner surface of the glass tube obtained under each condition. At 13 hours of immersion, there was an organopolysiloxane coating but no shape development (FIGS. 8a-b). However, in the system in which the immersion time was 36 hours, a dense nanoturf structure was expressed (FIGS. 9a-d). This suggests that a long soaking time is a necessary condition for the induction of the organopolysiloxane nanostructure from MTMS.

Examples 4-1 to 4-2
[Structure in which inner wall of glass tube is coated with polymer / organopolysiloxane nanostructure composite]
In Example 1, except that phenyltrimethoxysilane (PTMS) was used as a silane coupling agent, a structure having a glass inner wall coated was obtained in the same manner as in Example 1 (Table 4).

The glass tube end obtained through the above process was slightly crushed, and the fragments were observed with an SEM. 10 to 11 show the results of SEM photographs of the inner surface of the glass tube obtained under each condition. A clear nanoturf-like structure was developed after 7 hours of immersion (FIG. 10). In the system in which the immersion time was 22 hours, it was confirmed that the “grass leaf” structure of the turf had a tendency to become a hemispherical rod rather than a pointed structure (FIG. 11).

Example 5
[Structure in which inner wall of glass tube is coated with polymer / organopolysiloxane nanostructure composite]
In Example 1, the glass inner wall was formed in the same manner as in Example 1 except that a mixture (equal molar mixture) of mercaptopropyltrimethoxysilane (STMS) and vinyltrimethoxysilane (VTMS) was used as the silane coupling agent. A coated structure was obtained (Table 5).

The glass tube end obtained through the above process was slightly crushed, and the fragments were observed with an SEM. FIG. 12 shows the results of SEM photographs of the inner surface of the glass tube. Nano-turf structure was confirmed.

Example 6 and Comparative Example 1
[Structure of glass plate surface coated with polymer / organopolysiloxane nanostructure composite]
A thin film was prepared on the surface of a 3 × 2 cm soda glass plate using a spin coater (500 rpm / 2 seconds, 3000 rpm / 30 seconds) using a polystyrene sulfonic acid aqueous solution having a concentration of 0.5 wt%. After complete drying, it was immersed in an aqueous solution (80 ° C.) of 3 wt% L-PEI obtained in the above synthesis example and allowed to stand for 10 seconds. The plate was taken out, allowed to stand at room temperature for 5 minutes, and then immersed in an aqueous solution of STMS (STMS / water = 0.25 mL / 50 mL) for 15 hours. The plate was taken out, washed with distilled water and then dried in air. The surface of the film thus obtained was observed with an SEM (FIG. 13). It was confirmed that a dense nanoturf structure was formed as a whole.

As Comparative Example 1, instead of STMS of Example 6, tetramethoxysilane was used to prepare a mixed solution with water (10 mL silane / 50 mL water), and L- PEI adsorption glass slides were immersed and held at room temperature for 30 minutes. The glass plate was taken out, washed with distilled water and then dried in air. The film surface SEM image thus obtained is shown in FIG. It was confirmed to be a nano turf-like silica / polymer composite film as a whole.

The water contact angle and rubbing test of the surface of the two types of structures obtained in Example 6 and Comparative Example 1 were performed. The water contact angle of the surface film obtained in Example 6 was 74 ° and the surface showed hydrophobicity, whereas the water contact angle of the structure surface obtained in Comparative Example 1 was 0 ° and was superhydrophilic. Showed sex. Furthermore, using a non-woven fabric, a reciprocating rubbing test on the surface of the coating (reciprocating abrasion tester TYPE30S manufactured by HEIDON) was performed under a 10 g load condition. The structure surface (nano turf) containing the polysiloxane obtained in Example 6 was reciprocated 100 times, and then the aggregate part of the surface of the nano turf film was dropped and inserted into the turf layer surface. However, the structure of the nano turf layer was not broken (FIGS. 15a, b, c). Further, the hydrophobicity after the rubbing test was not changed, and the water contact angle was 71.5 °. On the contrary, in the case of the silica nanoturf film obtained in Comparative Example 1, the turf layer was completely crushed by rubbing 5 times and the water contact angle was improved to 34 °. This suggests that the two effects of silica nanoturf coating, silica absorption and lawn structure capillary effect, disappeared. From this comparison, it can be seen that, unlike silica brittleness, nanoturf containing organopolysiloxane exhibits sufficient toughness.

Claims

A nanostructure composite-coated structure in which the surface of a solid substrate (X) is coated with a nanostructure composite (Y), the nanostructure composite (Y) having a polyethyleneimine skeleton (a) A polysiloxane-containing nanostructure composite-covered structure comprising a polymer (A) and an organopolysiloxane (B).
The poly according to claim 1, wherein the nanostructure composite (Y) has a composite nanofiber (y1) as a basic unit, and the composite nanofiber is oriented substantially perpendicular to the surface of the solid substrate (X). Siloxane-containing nanostructure composite coated structure.
The nanostructure composite (Y) has composite nanofiber (y1) and / or composite nanoparticle (y2) as a basic unit, and the composite nanofiber (y1) and / or composite nanoparticle (y2) forms a network. The polysiloxane-containing nanostructure composite-coated structure according to claim 1, wherein the solid substrate (Y) is coated.
Step (1) of immersing the solid substrate (X) in a solution containing the polymer (A) having a polyethyleneimine skeleton (a) and then taking it out to form a polymer layer on the surface of the solid substrate (X) When,
The solid substrate (X) having the polymer layer obtained in the step (1) is brought into contact with a 0.05 to 0.5% by volume solution of the organoalkoxysilane (B ′) for 5 hours or more to obtain a solid group. A step (2) of depositing an organopolysiloxane (B) in the polymer layer on the surface of the material (X) to form a nanostructure composite (Y);
A process for producing a polysiloxane-containing nanostructure composite-covered structure, comprising:
The method for producing a polysiloxane-containing nanostructure composite-coated structure according to claim 4, wherein the organoalkoxysilane (B ') used in the step (2) is a silane coupling agent (b).
6. The polysiloxane-containing nanostructure composite-coated structure according to claim 5, wherein the organoalkoxysilane (B ′) has an organo group that is a mercaptopropyl group, a methyl group, a vinyl group, a glycidoxypropyl group, or a phenyl group. Production method.